Doping and coupling strength in molecular conductors: polyacetylene as a case study.

The doping mechanisms responsible for elevating the currents up to eleven orders of magnitude in semiconducting polymer films are today well characterized. Doping can also improve the performance of nanoscale devices or single molecule conductors, but the mechanism in this case appears to be different, with theoretical studies suggesting that the dopant affects the electronic properties of the junctions. In the present report, multiscale time-dependent DFT transport simulations help clarify the way in which n-type doping can raise the current flowing through a polymer chain connected to a pair of electrodes, with the focus on polyacetylene. In particular, our multiscale methodology offers control over the magnitude of the chemical coupling between the molecule and the electrodes, which allows us to analyze the effect of doping in low and strong coupling regimes. Interestingly, our results establish that the impact of dopants is the highest in weakly coupled devices, while their presence tends to be irrelevant in low-resistance junctions. Our calculations point out that both the equalization of the frontier orbitals with the Fermi level and a small gap between the HOMO and the LUMO must result from doping in order to observe any significant increase of the currents.